From: Eugen Leitl <eugen@leitl.org>
Date: Wed, Apr 18, 2012 at 10:28 AM
Subject: [tt] Juicers, Trippers, and Crocodiles: The Dangerous World
of Underground Chemistry
To: tt@postbiota.org
http://discovermagazine.com/2012/mar/08-juicers-trippers-crocodiles-dangerous-underground-chemistry/article_print
Juicers, Trippers, and Crocodiles: The Dangerous World of Underground
Chemistry
04.16.2012
Steroids, narcotics, and psychedelics are flowing freely from underground
labs around the world.
by Adam Piore
Nobody dreams of growing up and landing a low-paying job in New Jersey making
chemicals used in shampoos and hair gels. And on those long, tedious days
back in 1991 when a 24-year-old lab technician named Patrick Arnold stood
alone in a room stirring thickening agents into smelly vats of goo, there was
plenty of time to reflect on the twists of fate that had condemned him to
work in a place where "nothing interesting ever happened," in a job that was
"just going nowhere."
It took months to find the way out, but the path was there in front of him
all along. Arnold was an avid weight lifter, cursed with an average build
that had long ago stopped cooperating with his efforts to get bigger. Even
so, every night after work he would head to one of several gyms where he
pumped iron and talked shop with other muscleheads. The conversation would
often turn to anabolic steroids. Arnold had majored in chemistry at the
University of New Haven, and those weight-room discussions got him thinking.
One afternoon after starting the day's reactions at work, Arnold marched down
the hall to the chemistry library on his floor and looked up the molecular
structures of the steroids mentioned in his muscle magazines. Anabolic
steroids, which are essentially synthetic testosterone, had only just been
declared controlled substances, so there was still an awful lot of
information available about them.
It wasn't long before it hit him: "I hate my job, I'm sitting here, I've got
a lab—I can try making some of these things myself. No one will even know
what the hell I'm doing." Arnold added the steroid precursors he would need
to the regular list of laboratory chemicals he ordered through the company,
and nobody was the wiser.
Progress was slow at first. Often he would set out to make a product that he
knew should form a crystalline structure, only to end up with a sticky oil
stuck to a flask. To Arnold that residue was like a flashing "caution" sign,
an indication that potentially toxic impurities and leftover reactants had
failed to separate from the brew. But over time he became expert at using
solvents to wash the impurities and reactants away, and his compounds
increasingly came to form translucent, icelike crystals that indicated a high
level of purity.
Arnold's intellectual appetite grew with his mastery. Soon he was spending 10
hours a week visiting libraries, combing through obscure patents and research
journals for compounds with molecular structures worthy of further
exploration. Finally he settled on a recipe that he found in a 1930s-era
Swiss journal called Helvetica Chimica Acta and translated using a
German-English dictionary. It detailed the synthesis of mestanolone, one of
the first anabolic steroids ever made. Arnold figured it would make a good
first test, since its effects were widely known, unlike some of the more
exotic compounds he had come across.
In the lab Arnold watched the greenish byproducts wash out and pure crystals
form. When his lab's mass spectrometer showed a chemical profile identical to
the one he was seeking, he dissolved the compound in propylene glycol, an
odorless solvent that turned the mestanolone into a liquid. He put himself on
a regimen of 75 milligrams a day.
"There wasn't anything in there that was going to hurt me," he says. "But I
was cautious. I kept the dose at a reasonable level. I didn't do it for more
than a few weeks."
Some level of uncertainty is par for the course in the world of
do-it-yourself chemistry, which has seen the number of entrepreneurial
alchemists explode in the years since Patrick Arnold gulped down his first
chemical concoction and went on to become one of America's most notorious
underground chemists. It is a practice with a long history: In one form or
another, some chemists have been working outside the law since long before
the invention of the Bunsen burner. But the Internet has spawned a golden age
in bathtub chemistry. Never before has it been so easy to obtain the
instructions, the precursor molecules, and the manufacturing capabilities to
produce exotic, unregulated compounds on a mass scale—or print out crude
recipes for drugs you can make yourself. As a result, a new generation of
Internet-savvy entrepreneurs is unleashing an ever-changing array of products
into the shadowy drug bazaars of cyberspace, while dope fiends readily brew
up simpler compounds in their kitchens.
The new DIY substances range from a vast inventory of performance-enhancing
drugs consumed by gym rats looking to get big, to an ever-growing selection
of psychoactive compounds sampled by club-hopping teenagers, to synthetic
variations of hard-core narcotics wolfed down by desperate drug addicts. The
consumers experimenting with these unregulated chemical concoctions may
inhabit different worlds—the gym, the rave, and the crash house,
respectively—but the drugs themselves are often produced with precursors
purchased from the same places and derived from recipes traded on many of the
same websites. They also carry some of the same risks.
The skill levels and attitudes of these bathtub chemists vary widely,
including not only the studious, research-driven types like Arnold but also
the callously reckless and the criminally stupid. And the list of what can go
wrong with home-brewed compounds is long. A horrific example comes from the
Internet-directed chemical explorations of ambitious methamphetamine users.
In attempting to synthesize crystal meth, these do-it-yourselfers have caused
a rash of trailer park explosions and often unwittingly produce a drug coated
with toxins like hydroiodic acid. The best way to remove those noxious
byproducts is by washing the drug in alcohol using a Büchner funnel, a
specialized lab vacuum. But most kitchen chemists have never even heard of
it. When this final purification step is skipped, the toxins eat away at the
user's gums, teeth, and inner lining of the cheeks, resulting in a toothless,
hollowed-out condition known as "meth mouth."
But the fastest-growing trend is a more complicated class of compounds brewed
up by trained chemists like Patrick Arnold who are searching for exotic
steroids or pursuing novel psychoactive compounds. In just the past two
years, the use of synthetic stimulants that produce a methlike high and are
marketed as "bath salts" has exploded. In 2010 alone, 41 new psychoactive
substances were reported by European nations—more than triple the amount
identified in 2008, according to a report issued by the European Monitoring
Centre for Drugs and Drug Addiction. (No similar statistics are kept in the
United States, but many of the drugs end up here, too.) The new substances
include derivatives of PCP and cocaine, as well as new forms of synthetic
cannabinoids, compounds that are similar to tetrahydrocannabinol, the active
ingredient in marijuana. +++
Many of these psychoactive substances are little-known compounds culled from
obscure research journals like Arnold's Swiss periodical. While some
published steroids have a research trail, most psychoactive drugs have never
been tested on humans—until, that is, they show up at clubs or parties. When
these recipes hit the mainstream, they often go viral through websites where
chemists and entrepreneurs of all stripes trade recipes.
These drugs can end up being mass-produced by chemists for hire in China, who
advertise "custom organic synthesis" on the web and take their orders from
the emerging breed of transnational rogue chemists. "There are a lot of very,
very smart people out there who know how to read chemistry papers," says
Nathan Messer, president of the nonprofit organization DanceSafe, which
provides drug testing at festivals and parties. "It usually starts off as
some people making it themselves, and if it works out, they will contract it
out to China, set up a distribution chain, buy in bulk, and sell it."
What effect these new, unregulated psychoactive drugs might have on the human
body is typically not clear. Often they are chosen because their chemical
structures resemble those of known illegal drugs, like MDMA (ecstasy), speed,
or cocaine, but are just different enough that they can arguably be
considered legal, or can be marketed in the United States as "not for human
consumption" with a hint of credibility. Some vendors hope this distinction
will allow them to evade a 1970 law that allows authorities to prosecute for
drugs that are "substantially similar" to banned substances if they are
intended for human consumption.
For underground chemists gearing their efforts to the parallel market for
performance-enhancing drugs, tweaking a couple atoms—or brewing up an obscure
compound most people aren't aware exists—can render a banned substance
undetectable to professional sporting bodies, since they need a reference
sample to spot it.
This kind of kitchen chemistry can have devastating results. Throughout the
1970s and 1980s, dozens of drug users consumed homemade batches of a
synthetic opiate called MPPP that gave them symptoms of Parkinson's. The
cause was a mundane chemistry error. The pH during one of the reactions was a
bit too low, causing the drug to extrude a single small molecule of propionic
acid, which transformed it from a powerful narcotic into a poison that laid
waste to the brain's dopamine receptors.
David Nichols, a professor in Purdue University's pharmacology department,
knows firsthand what can happen when research chemicals find their way into
underground labs. He has spent decades feeding LSD, mescaline, and MDMA
derivatives to rats in an effort to map the brain receptors they act upon. He
works by tweaking the chemical structures of the drugs, sometimes changing
just a few molecules to see what impact this might have on the interaction
between the drug and the brain receptors their parent compounds normally act
upon.
There are a lot of very, very smart people out there who know how to read
chemistry papers. It usually starts off as some people making it themselves."
Nichols first became aware that rogue chemists were following his research
more than 10 years ago, when one of his ecstasy derivatives called
4-methylthioamphetamine (MTA) appeared in Europe as a club drug. In a
published paper, Nichols had reported that rats that had been trained to
press a lever when administered MDMA also hit the button when given MTA. That
apparently was enough to catch the attention of a rogue chemist who
synthesized the drug, rechristened it Flatliners, and sold it in the
Netherlands. The choice of name was a morbid harbinger. By 2002 Flatliners
had killed at least six people. Nichols believes they died from an overdose
of the neurotransmitter serotonin, which can lead to hyperthermia, muscle
breakdown, and seizures.
Flatliners, it turns out, does not release the dopamine and norepinephrine
that account for much of ecstasy's euphoric effects, but, like ecstasy, it
does release massive doses of serotonin and interferes with the body's
efforts to break it down. That apparently accounted for the reaction Nichols
recorded in rats, which recognized the serotonin rush caused by MDMA. Nichols
believes that when the initial dose of Flatliners failed to produce the
ecstasy-like euphoria the human drug users were expecting, they upped their
dosage—and kept upping it until it killed them.
Tragic as the deaths were, Nichols is more worried about what might happen if
underground compounds cause side effects that are less obvious and take
longer to manifest. "That is my biggest fear," he says. "Suppose somebody
makes something like ecstasy? That's a big success for them. But nothing is
known about how the drug reacts with the rest of the body. Suppose it kills
cells in the pancreas or in another organ? And suppose people take it every
weekend? If a couple of people die, that is not nearly the tragedy if a
hundred thousand people suddenly needed heart transplants."
Mike Cole, a forensic scientist at Anglia Ruskin University in Cambridge,
England, has done research that indicates Nichols is right to be concerned.
Cole has been studying a drug developed to combat parasitic worms in
livestock. Now mass-produced in East Asia, it is peddled in the party scenes
of San Francisco and elsewhere as a "legal" and "safe" alternative to
ecstasy. The drug, benzylpiperazine, isn't difficult to make; it requires a
chemist to trigger a reaction between two chemicals in a flask, then cool
them down until the compounds combine into crystals and the drug precipitates
out.
But the drug, Cole demonstrated in his lab, can be highly toxic to the
kidneys. "If you worked for a chemical company, you would clean up your final
product," he says. "But the guys on the street aren't interested in it.
They're trying to make maximum profit, and you can get the effects without
the cleanup process."
Meanwhile, many bodybuilding steroids have been shown to cause liver and
kidney disorders and male infertility. The likelihood these side effects will
occur is dependent on the potency and dosage of the compounds consumed, and
the less one knows about the steroid in question, the harder it is to get the
dosage right. The impact of years of doping is even more difficult to
determine. "We have yet to do an epidemiological study of long-term effects,"
says Penn State professor emeritus Charles Yesalis, one of the foremost
experts on steroids. "And if we don't know the long-term health effects of
the known drugs produced by pharmaceutical companies, we sure as heck aren't
going to know the effects of the unknown ones."
+++
A week after Arnold took his first dose of liquid mestanolone, his life began
to change. At the gym, he was on fire. The amount he could bench-press spiked
and kept rising, topping out at 30 extra pounds. Soon his clothes were
tighter, and his muscles popped with new veins. The physical transformation
was hard to ignore, and Arnold confessed his actions to his office friends.
"It got around; everybody found out," Arnold recalls. "But I didn't give a
damn."
Arnold left his job, moved back to Connecticut, and started taking
graduate-level chemistry classes at the state university. He also joined an
Internet discussion group on fitness and weight lifting. Arnold's knowledge
of steroids quickly set him apart from other members of the discussion group.
People began to seek his advice.
One of them was former bodybuilder Dan Duchaine, the author of The
Underground Steroid Handbook, an indispensable reference manual for juicers.
He had also served two prison stints for trafficking in steroids. Duchaine
was well connected in the emerging field of gray-market nutritional
supplements, products that often pushed the limits of laws regulating
steroids. Through a friend, he put Arnold in touch with a Trinidadian
entrepreneur, Ramlakhan Boodram, who owned a company that sold soy-processing
and farm equipment in Champaign, Illinois, and had manufactured a nutritional
supplement for Duchaine's friend. Boodram was hoping to break into the
booming field himself and needed a chemist to develop products for him.
Arnold moved to the Midwest. There, surrounded by cornfields, he set up a lab
in an old brick warehouse that was crammed with tractors, metal presses, and
oversize mixers used to process soy. He started out with just a few flasks
and a hot plate, but eventually he filled his corner of the building with a
mass spectrometer, vacuum pump, and all the lab equipment he would need to
brew up new substances. Arnold focused his efforts on a patent he came across
while flipping through chemical abstracts. It came from an East German
pharmaceutical company called Jenapharm, which produced most of the steroidal
compounds used in the former communist nation's athletic doping program.
Jenapharm's patent concerned a compound known as androstenedione, a naturally
occurring testosterone precursor produced by the adrenal glands, testicles,
and ovaries. Synthesized andro was widely used in labs as a steroid
precursor. But the patent noted that if you administered the hormone orally,
the body's own enzymes would catalyze reactions that would convert it to
testosterone, theoretically providing performance-enhancing benefits similar
to those of steroids derived from the substance in the lab.
Andro would be potent, easy to make, and possibly legal; after all, Arnold
reasoned, how can you regulate something that occurs naturally in the body?
Still, he knew it would push legal boundaries to sell something that would
turn into a banned substance once ingested. He worried he might get arrested.
As an entrepreneur trying to break into nutritional supplements, he decided
to take the risk anyway. "Nobody was going to buy vitamins from me," Arnold
says. "When you're trying to start a business from nothing, you have to have
something unique to sell."
Once andro hit the market, word of its potency spread quickly through the
athletic community. Then a reporter spotted a vial of the supplement in the
locker of baseball slugger Mark McGwire during the season when he shattered
the 37-year-old single season home run record. Suddenly Arnold was famous. In
1998 Sporting News named him number 84 on its list of the 100 most powerful
people in sports, sandwiched between sportscaster Bob Costas and superagent
Arn Tellem.
Arnold moved to cash in on his renown. He went back to the journals, scanning
abstracts for other naturally occurring metabolites that looked likely to be
converted into testosterone once ingested. He came out with several more
so-called prohormones. In 2003 he and his partners moved to a shiny new
38,000-square-foot warehouse with 30-foot ceilings, 2,000-gallon reactors,
and a state-of-the-art research lab with a gas chromatograph and other
analytic instrumentation. By 2004 their revenues hit $12 million a year.
Secretly Arnold continued to experiment with illegal steroids. Back in New
Jersey, he had come across an anabolic steroid he'd never seen anywhere else,
a compound that had been developed by Wyeth Pharmaceuticals (now owned by
Pfizer) in the early 1960s. Called norbolethone, it had a unique chemical
structure that would be impossible to detect, but it also seemed to have many
characteristics of the more potent steroids Arnold had tried. Back then, as a
lowly lab tech at a chemical company, Arnold could never get hold of the
precursor, a prohibitively expensive synthetic progestogen known as
levonorgestrel, the active ingredient in the morning-after pill.
One day, talking to a business associate at another nutritional supplements
company, Arnold mentioned norbolethone and his problems getting the
precursor. Soon afterward, a gift arrived in the mail from China: a package
of levonorgestrel. Arnold brewed up a batch of norbolethone, cross-checked
the molecular structure with his instruments, and gave himself a mild dose.
Arnold rationalized that the compound was probably safe. "One dose of a
steroid will never kill you, even if it is massive," he later explained.
Whereas psychoactive drugs can have immediate unpredictable and dramatic
effects, steroids work primarily by activating genes, a slow process that
only gradually yields detectable physiological effects. "Only with chronic
intake will you see adverse effects from a steroid," Arnold says. He did
notice the compound turned his urine a dark shade of yellow, which led him to
believe it might be placing a strain on his liver. On the other hand, he was
on fire again at the gym. It was potent stuff.
As a side job, Arnold gave phone consultations for people aiming to bulk up,
which he advertised on a bodybuilding website. If a client inquired about
untraceable steroids, Arnold would send him samples of his compound. "I must
emphasize," he would later say, "that I made everyone aware these drugs had
potential long-term adverse effects."
That such a potent steroid could be so easily distributed alarms Gordon
Hughes, who invented norbolethone in 1961 as part of his Ph.D. thesis at the
University of Manchester in England. While employed by Wyeth, he developed
the compound to help elderly surgery patients who needed to build more
protein; he never imagined it might someday be used by athletes. "It bothers
me that people are getting these drugs," Hughes says. "You don't know how
pure they are. They haven't passed FDA requirements. You don't know anything
about them."
That is a sentiment shared by plenty of other research chemists. Clemson
University professor emeritus John W. Huffman devoted 27 years of his career
to developing biological analogues to THC, the principal active component of
marijuana. Huffman hoped to understand how THC and related compounds interact
with brain receptors and perhaps find treatments for nausea and glaucoma.
In 2008 he learned his chemicals were being marketed as "legal" highs in
Germany. "There have been some rather severe cases of psychosis," he sighs.
"I figure people are responsible for their own actions. If they use this
stuff, which they shouldn't, they are going to suffer the consequences." +++
Just as Arnold suspected, norbolethone was so obscure that professional
doping programs had no reference sample and thus could not detect it. It was
a brash entrepreneur named Victor Conte who pushed the limits of that
obscurity. He ran a sports-nutrition center in Burlingame, California, called
the Bay Area Laboratory Co-operative (BALCO). Through BALCO, Conte sold legal
zinc-magnesium supplements of questionable efficacy and enlisted topflight
athletes to promote them. Among them were true superstars: Marion Jones, who
would become the fastest woman in the world, and Barry Bonds, who would go on
to break the record for most home runs in a single season. In addition to
providing these athletes with supplements, Conte offered up secret supplies
of illegal steroids on the side.
Arnold, who met Conte in an Internet chat group, sent him the new compound.
Conte rechristened it "the clear" and began distributing it to top athletes.
Arnold himself gave the clear to Olympic cyclist Tammy Thomas, whose heavy
use would eventually alert authorities to the drug. Thomas ignored Arnold's
dosing advice, he claims, and by 2002 was using so much norbolethone that she
had grown facial hair. When her natural testosterone dropped to levels far
below normal, testers began to scrutinize her urine. It was only a matter of
time before they identified metabolites that led them to norbolethone.
Conte got wind that the authorities were closing in and told Arnold to find a
replacement compound. In response, Arnold gambled with a move both rare and
bold in underground chemistry: He created an entirely new steroid. To do so,
he sat down with The Merck Index, a standard reference manual for chemicals,
drugs, and other compounds, and turned to the section on the class of
hormones to which norbolethone's precursor belonged. He hoped to find a
different precursor that could be transformed into a steroid using the same
molecular processes used to render norbolethone.
Arnold dismissed some because he knew they were associated with steroids on
watch lists. Others he knew from experience had molecular properties that
would make them weak. Then he spotted tetrahydrogestrinone, a compound never
before used to create a steroid. It had three alternating carbon double
bonds, called conjugations, that he had seen in some potent steroids, as well
as an additional carbon atom that he recognized would give it extra strength.
"I knew I was looking at an exciting structure," Arnold recalls. "It's very
complex compared with other ones. It was more potent. People would not have
to take as much. The stuff would have been invisible forever. It was perfect,
perfect stuff." He put clients on 10 milligrams a day, then reduced it to 5
milligrams when he was sure it worked.
But Conte had a lot of enemies, among them Marion Jones's former coach Trevor
Graham. In June 2003 Graham sent a syringe that contained the new substance
to the U.S. Anti-Doping Agency. Once the group had a sample, it was only a
matter of time. The authorities closed in and exposed one of the biggest
scandals in the history of sports.
In 2005 the Feds raided Arnold's home and lab. He was convicted and sentenced
to three months in prison in 2006. The investigation touched off litigation
that lasted through last year, when Barry Bonds was finally sentenced to 30
days of house arrest for obstructing justice during the inquiry.
Today, Arnold insists he is out of the steroid game. Andro and many other
prohormones like it have been outlawed by Congress, and Arnold says he is
focused solely on legal supplements. To pay fines, he and his partner were
forced to auction off their new warehouse with all its top-of-the-line
equipment. Today they are back in the old warehouse in the cornfields outside
of Champaign, looking for compounds that are distinct from any banned
substances to keep them out of trouble.
I knew I was looking at an exciting structure, very complex compared with
other ones. It was more potent. The stuff would have been invisible forever."
Don Catlin, the founder of the UCLA Olympic Analytical Laboratory in Los
Angeles and the man who finally identified Arnold's "clear," says there are
several hundred known steroids, and one could "spend a lifetime finding them,
manipulating them, and getting them into a form where you could give them to
a human being."
Arnold says that in manufacturing their own supplements, he and Boodram are
now an exception in the industry. Almost nobody makes steroids or supplements
themselves nowadays; most outsource the job to China. As a respected
underground chemist, Arnold is sometimes called upon by others in the
industry to test products they have had made in Chinese factories. He says
these factories "often substitute cheaper steroids for more expensive ones,
or sometimes they just sell crap, which I can't even characterize on my
instruments."
The same problem shows up in the new wave of psychoactive chemicals
mass-produced overseas. At least five deaths and dozens of hospitalizations,
for instance, are believed to have been caused by a compound called
Bromo-Dragonfly that was first developed in Nichols's Purdue lab and is now
produced for Westerners in China.
In one fatal 2009 batch, a San Jose man died after consuming Chinese-made
Bromo that contained "unspecified synthesis impurities," which may have
contributed to the product's toxicity, according to the underground drug user
website Erowid. His distributor sent more of that batch to other users in
Denmark and Spain, leading to at least one other death and numerous
hospitalizations. And just last May, a Chinese manufacturer sent a college
student in Oklahoma a mislabeled batch of Bromo when he had ordered a far
less potent product. As a result, two more people died and six others were
hospitalized after overdosing.
The shifting realities of a world where legitimate chemical research can be
hijacked by anyone with a hot plate and an Internet connection has forced
Nichols to reconsider his craft. He works more closely with the Drug
Enforcement Agency to monitor new compounds and is more aware of the
consequences of making his research public. "Now when we publish, I think,
'Is this going to be a problem?' If we published an LSD analogue with 10
times the potency of LSD, I guarantee that six months later it would be all
over the Internet."
Nichols believes his work could help explain memory, depression, even the
nature of consciousness. Science must continue, he says, and he can't stop
publishing. But now he knows who might be reading.
Adam Piore is a DISCOVER contributing editor. He last wrote for the magazine
on regenerative medicine in the July/August 2011 Issue.
Russia's Home-Brewed Drug Crisis
Crystal meth, synthesized in small-scale labs across the United States,
exacts a harsh physical toll, rotting users' gums and eating away at their
teeth. But meth's ill effects pale in comparison to those of an intravenous
home-brewed opiate now sweeping through Russia. The drug's nickname,
krokodil, comes from a grisly sign of use: Tissue around the injection site
dies and results in patches of skin that turn greenish gray and scaly, like
the hide of a crocodile.
Desomorphine, as krokodil is formally known, can be cooked up at home
according to online recipes that require only readily available ingredients.
Codeine, the active component, is sold over the counter in Russia in cough
medicines and painkillers. Other components are household items, including
paint thinner, iodine, and red phosphorus shaved from matchbooks.
"Krokodil is a last resort for people who can't get heroin or other injected
drugs," says Russian public-health researcher Kirill Danishevskiy. It costs
only a tenth as much as heroin, though its high is shorter; addicts often
have to inject the drug 7 to 10 times a day to stave off withdrawal.
Although statistics are scarce, Russia—a nation of about 140 million
people—may have nearly a million krokodil users, estimates Anya Sarang, a
public-health advocate who works with drug users in Moscow.
The drug's toxicity has effects much grimmer than crocodile-like skin. Large
areas of tissue can rot away, often down to the bone; in severe cases, the
bone rots away, too. Addicts are often forced to have their limbs amputated
and are prone to secondary infections such as tuberculosis. But many users
are so caught up in the cycle of making and taking the drug, Sarang says,
that they cannot be bothered to go to a doctor—and for the few who do,
Russian hospitals are ill equipped to help them. Life expectancy for krokodil
addicts after they begin using is about two years.
—Valerie Ross
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